Solar cell modules with improved backsheet

ABSTRACT

Disclosed is a polyamide-ionomer composition suitable for use in a backsheet in a photovoltaic module comprising a polymer component a polyamide and an anhydride ionomer comprising a copolymer of ethylene, an alpha, beta-unsaturated C 3 -C 8  carboxylic acid and an ethylenically unsaturated dicarboxylic acid or derivative thereof selected from the group consisting of maleic acid, fumaric acid, itaconic acid, maleic anhydride, and a C 1 -C 1  alkyl half ester of maleic acid, wherein the carboxylic acid functionalities present are at least partially neutralized to carboxylate salts of one or more alkali metal, transition metal, or alkaline earth metal cations; 0 to 20 weight % of pigment; and 0 to 40 weight % of filler; preferably wherein the combination of pigment and filler comprises 10 to 50 weight % of the composition; and 0 to 5 weight % of weatherability additives.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) from U.S.Provisional Patent Application No. 61/985,579, filed Apr. 29, 2014,hereby incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to photovoltaic solar cell modules having animproved backsheet.

BACKGROUND OF THE INVENTION

A common form of solar cell module or photovoltaic (PV) module is madeby interconnecting individually formed and separate solar cells, e.g.,crystalline silicon solar cell, and then mechanically supporting andprotecting the cells against environmental degradation by integratingthe cells into a laminated solar cell module. The laminated modulesusually comprise a stiff transparent protective front panel or sheet,and a rear panel or sheet typically called a “backsheet” or “backskin”.Interconnected solar cells and an encapsulant are disposed between thefront and back sheets so as to form a sandwich arrangement. A necessaryrequirement of the encapsulant (or at least that portion thereof thatextends between the front sides of the cells and the transparent frontpanel) is that it be transparent to solar radiation. The typical mode offorming the laminated module is to assemble a sandwich comprising inorder a transparent panel, e.g., a front panel made of glass or atransparent polymer, a front layer of at least one sheet of encapsulant,an array of solar cells interconnected by electrical conductors (withthe front sides of the cells facing the transparent panel), a back layerof at least one sheet of encapsulant, a sheet of scrim to facilitate gasremoval during the lamination process, and a backsheet or back panel,and then bonding those components together under heat and pressure usinga vacuum-type laminator. The back layer of encapsulant may betransparent or any other color, and prior art modules have been formedusing a backsheet consisting of a thermoplastic polymer, glass or someother material.

Although the lamination process seals the several layered componentstogether throughout the full expanse of the module, it is commonpractice to apply a protective polymeric edge sealant to the module soas to assure that moisture will not penetrate the edge portion of themodule. The polymeric edge sealant may be in the form of a strip of tapeor a caulking-type compound. Another common practice is to provide themodule with a perimeter frame, usually made of a metal like aluminum, toprovide mechanical edge protection. Those techniques are disclosed orsuggested in U.S. Pat. No. 5,741,370. That patent also discloses theconcept of eliminating the back layer of encapsulant and bonding athermoplastic backskin directly to the interconnected solar cells.

A large number of materials have been used or considered for use as theencapsulant in modules made up of individual silicon solar cells. Untilat least around 1995, ethylene vinyl acetate copolymer (commonly knownas “EVA”) was considered the best encapsulant for modules comprisingcrystalline silicon solar cells. However, EVA has certain limitations:(1) it decomposes under sunlight, with the result that it discolors andgets progressively darker, and (2) its decomposition releases aceticacid which in turn promotes further degradation, particularly in thepresence of oxygen and/or heat.

U.S. Pat. No. 5,478,402 discloses use of an ionomer as a cellencapsulant substitute for EVA. The use of ionomer as an encapsulant isfurther disclosed in U.S. Pat. No. 5,741,370. Ionomers are acidcopolymers in which a portion of the carboxylic acid groups in thecopolymer are neutralized to salts containing metal ions. U.S. Pat. No.3,264,272 discloses a composition comprising a random copolymer ofcopolymerized units of an alpha-olefin having from two to ten carbonatoms, an alpha, beta-ethylenically-unsaturated carboxylic acid havingfrom three to eight carbon atoms in which 10 to 90 percent of the acidgroups are neutralized to salts with metal ions from Groups I, II, orIII of the Periodic Table, notably, sodium, zinc, lithium, or magnesium,and an optional third mono-ethylenically unsaturated comonomer such asmethyl methacrylate or butyl acrylate.

It is known to use a rear panel or backsheet that is made of the samematerial as the front panel, but a preferred and common practice is tomake it of a different material, preferably a material that weighssubstantially less than glass, such as a polyvinyl fluoride polymeravailable under the tradename Tedlar® from E.I. Du Pont de Nemours Co.(DuPont). A widely used backsheet material is aTedlar®/polyester/ethylene vinyl acetate laminate. Another commonbacksheet uses a trilayer structure of Tedlar®/Polyester/Tedlar®, alsocalled TPT™, described in WO 94/22172. This structure allows thefluoropolymer to protect both sides of the polyester fromphoto-degradation. However, Tedlar® and Tedlar® laminates are nottotally impervious to moisture, and as a consequence over time the poweroutput and/or the useful life of modules made with this kind ofbacksheet material is reduced due to electrical shorting resulting fromabsorbed moisture.

Due to the price and the supply concern, the PV industry has beengradually evaluating new alternatives, such as backsheets derived fromPET, polyamides, etc. For example, WO 2008/138021 discloses PV moduleswith backsheets based on polyamides derived from linear and/or branchedaliphatic and/or cycloaliphatic monomers, which have an average of atleast 8 and most 17 carbon atoms, such as nylon 12. However, polyamidesare semi-crystalline polymers with high degree of crystallinity, whichcan lead to brittleness, low flexibility and excessive shrinkage. Highmoisture absorption is especially a problem for nylon-6 and nylon-66,the most inexpensive polyamides. Water absorption causes dimensionalinstability, poor weatherability, and, most importantly, reducesinsulation capability. While nylon-11 and nylon-12 have better moistureresistance and weatherability, the melting temperature may be too lowfor use in some lamination processes of PV module assembly.

U.S. Pat. No. 5,741,370 discloses using as the backskin material athermoplastic olefin comprising a combination of two different ionomers,e.g., a sodium ionomer and a zinc second ionomer, with that combinationbeing described as producing a synergistic effect which improves thewater vapor barrier property of the backskin material over and above thebarrier property of either of the individual ionomer components. Thepatent also discloses use of an ionomer encapsulant with the dualionomer backskin.

It is known that thermoplastic blends or alloys based on ionomers andpolyamides have a combination of desirable properties (see U.S. Pat.Nos. 4,174,358, 5,688,868, 5,866,658, 6,399,684, 6,569,947, 6,756,443and 7,144,938, 7,592,056, 8,057,910, 8,062,757 and 8,119,235). Forexample, U.S. Pat. No. 5,866,658 discloses a blend of an ionomerdispersed in a continuous or co-continuous polyamide phase in the rangeof 60/40 weight % to 40/60 weight % used for molded parts exhibitingtoughness, high gloss, abrasion/scratch resistance, and high temperatureproperties. U.S. Pat. No. 6,399,684 discloses similar blends alsocontaining phosphorous salts such as a hypophosphite salt. See also U.S.Patent Applications 2002/0055006, 2005/007462, 2006/0142489,2008/0161503, 2009/0298372, 2013/0167966, 2013/0171390, 2013/0171394,2013/0172470 and 2013/0172488.

U.S. Pat. Nos. 5,700,890, 5,859,137, 7,267,884 and U.S. PatentApplication Publications 2005/0020762A1, and 2006/0142489A1 disclosepolyamides toughened with ionomers of ethylene copolymers containing amonocarboxylic acid and a dicarboxylic acid or derivative thereof. U.S.Patent Application Publication 2011/0020573 discloses a blend comprisinga polyamide, an ionomer of an ethylene copolymer containing amonocarboxylic acid and a dicarboxylic acid or derivative thereof, and asulfonamide. U.S. Pat. No. 8,586,663 discloses a blend comprising apolyamide, an ionomer of an ethylene copolymer containing amonocarboxylic acid and a dicarboxylic acid or derivative thereof, and asecond ionomer. U.S. Pat. No. 7,592,056 discloses blends of polyamideswith mixed ion ionomers, including zinc and sodium mixtures.

U.S. Pat. No. 6,660,930 discloses photovoltaic modules comprisingbackskins comprising a nylon/ionomer alloy.

Photovoltaic modules can be assessed for moisture permeation andweatherability by cyclic treatment with high moisture and temperatureand cold temperature in standardized “stress tests”. It is desirable toprovide PV modules that are capable of withstanding such stress testsfor substantially more than 1000 hours. Thus, it also is desirable toprovide backsheet materials that provide PV modules that are capable ofwithstanding such stress tests.

SUMMARY OF THE INVENTION

This invention relates to a polyamide-ionomer composition suitable foruse in a backsheet in a photovoltaic module.

The polyamide-ionomer blend composition comprises, or consistsessentially of

-   -   (i) A polymer component comprising, or consisting essentially of    -   1) 53 to 64 weight %, based on the combination of (1) and (2),        of a polyamide;    -   2) 36 to 47 weight %, based on the combination of (1) and (2),        of an anhydride ionomer comprising, or consisting essentially of        a copolymer of        -   (a) ethylene;        -   (b) from 5 weight % to 15 weight % of an alpha,            beta-unsaturated C₃-C₈ carboxylic acid;        -   (c) from 0.5 weight % to 12 weight % of at least one            comonomer that is an ethylenically unsaturated dicarboxylic            acid or derivative thereof selected from the group            consisting of maleic acid, fumaric acid, itaconic acid,            maleic anhydride, and a C₁-C₄ alkyl half ester of maleic            acid; and        -   (d) from 0 weight % to 30 weight % of monomers selected from            alkyl acrylate and alkyl methacrylate, wherein the alkyl            groups have from one to twelve carbon atoms; wherein the            carboxylic acid functionalities present are at least            partially neutralized by one or more alkali metal,            transition metal, or alkaline earth metal cations;    -   (ii) 0 to 20 weight % of pigment; and    -   (iii) 0 to 40 weight % of filler; preferably wherein the        combination of (ii) and (iii) comprises 8 to 50 weight % of the        combination of (i), (ii), (iii) and (iv); and    -   (iv) 0 to 5 weight % of additives selected from oxidation        inhibitors, UV stabilizers, and hindered amine light        stabilizers.

The invention provides a backsheet for a photovoltaic module comprisingor consisting essentially of the composition described above.

The invention also provides a laminated solar cell module comprising orconsisting essentially of a front support layer formed of a lighttransmitting material and having first and second surfaces; a pluralityof interconnected solar cells having a first surface facing the frontsupport layer and a second surface facing away from the front supportlayer; a transparent encapsulant surrounding and encapsulating theinterconnected solar cells, the transparent encapsulant being bonded tothe second surface of the front support layer; and a backsheet asdescribed above wherein one surface of the backsheet is bonded to thesecond surface of the transparent encapsulant.

The invention also provides an assembly for conversion under heat andpressure into a laminated solar cell module, the assembly comprising afront support layer formed of a light transmitting material and havingfront and back surfaces; a first transparent thermoplastic encapsulantlayer adjacent to the back surface of the front support layer; aplurality of interconnected solar cells having first and second surfacesadjacent to the first transparent encapsulant layer; a secondtransparent thermoplastic encapsulant layer disposed adjacent to thesolar cells in parallel relation to the first transparent encapsulantlayer; and a thermoplastic backsheet as described above.

The invention also provides a method of manufacturing a solar cellmodule comprising providing a front support layer formed of a lighttransmitting material and having front and back surfaces; placing afirst transparent thermoplastic encapsulant layer adjacent to the backsurface of the front support layer; positioning a plurality ofinterconnected solar cells having first and second surfaces so that thefirst surfaces thereof are adjacent to the first transparent encapsulantlayer; placing a second transparent thermoplastic encapsulant layeradjacent to the second surfaces of the solar cells; placing a backsheetas described above adjacent to the second transparent thermoplasticencapsulant layer to thereby form an assembly; subjecting the assemblyto heat and pressure so as to melt the encapsulant layers and cause theencapsulant to surround the solar cells, and cooling the assembly so asto cause the encapsulant to solidify and bond to the front supportlayer, the solar cells and the backsheet, thereby laminating the layersand the solar cells together to form an integrated solar cell module.

DETAILED DESCRIPTION OF THE INVENTION

All publications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent). As used herein, the terms “a” and “an” include the concepts of“at least one” and “one or more than one”.

Unless stated otherwise, all percentages, parts, ratios, etc., are byweight. Further, when an amount, concentration, or other value orparameter is given as either a range, preferred range or a list of upperpreferable values and lower preferable values, this is to be understoodas specifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether ranges are separately disclosed. Where arange of numerical values is recited herein, unless otherwise stated,the range is intended to include the endpoints thereof, and all integersand fractions within the range. It is not intended that the scope of theinvention be limited to the specific values recited when defining arange. When a component is indicated as present in a range starting from0, such component is an optional component (i.e., it may or may not bepresent). When present an optional component may be at least 0.1 weight% of the composition or copolymer.

When materials, methods, or machinery are described herein with the term“known to those of skill in the art”, “conventional” or a synonymousword or phrase, the term signifies that materials, methods, andmachinery that are conventional at the time of filing the presentapplication are encompassed by this description. Also encompassed arematerials, methods, and machinery that are not presently conventional,but that may have become recognized in the art as suitable for a similarpurpose.

As used herein, the term “copolymer” refers to polymers comprisingcopolymerized units resulting from copolymerization of two or morecomonomers and may be described with reference to its constituentcomonomers or to the amounts of its constituent comonomers such as, forexample “a copolymer comprising ethylene and 15 weight % of acrylicacid”. A description of a copolymer with reference to its constituentcomonomers or to the amounts of its constituent comonomers means thatthe copolymer contains copolymerized units (in the specified amountswhen specified) of the specified comonomers.

In this application, the terms “sheet”, “layer” and “film” are used intheir broad sense interchangeably to describe articles wherein thecompositions are processed into generally planar forms, either monolayeror multilayer. The processing method and/or the thickness may influencewhether the term “sheet” or “film” is used herein, but either term canbe used to describe such generally planar articles.

A “frontsheet” is a sheet, layer or film positioned as the outermostlayer on the side of a photovoltaic module that faces a light source andmay also be described as an incident layer. Because of its location, itis generally desirable that the frontsheet has high transparency to thedesired incident light to allow efficient transmission of sunlight intothe solar cells. It is also desirable that the frontsheet has highmoisture barrier properties to prevent entry of moisture into thephotovoltaic module. Such moisture intrusion can degrade thephotovoltaic module components and/or reduce the electrical efficiencyof the module.

A “backsheet” is a sheet, layer or film on the side of a photovoltaicmodule that faces away from a light source, and is often opaque. In someinstances, it may be desirable to receive light from both sides of adevice (e.g. a bifacial device), in which case a module may havetransparent layers on both sides of the device.

“Encapsulant” layers are layers used to encase the fragilevoltage-generating solar cell layer to protect it from damage and holdit in place in the photovoltaic module and are normally positionedbetween the solar cell layer and the incident layer and the backinglayer. Suitable polymer materials for these encapsulant layers typicallypossess a combination of characteristics such as high transparency, highimpact resistance, high penetration resistance, high moistureresistance, good ultraviolet (UV) light resistance, good long termthermal stability, adequate adhesion strength to frontsheets,backsheets, and other rigid polymeric sheets and cell surfaces, and goodlong term weatherability.

This invention involves the use of a polyamide-ionomer alloy in sheetform as a backsheet material. As used herein, the term “alloy” is usedto describe a polymer blend that forms a distinct polymer substance.Various polyamide-ionomer alloys are available. The composition limitsas defined in the Summary of the Invention above provide that thefraction of polyamide is sufficient to ensure the polyamide remains thecontinuous phase during alloying and subsequent converting to film andthe fraction of the ionomer is sufficient to ensure adequate toughnessas made and after aging as well as good adhesion to the encapsulant.

Thermoplastic resins are polymeric materials that can flow when heatedunder pressure. Melt index (MI) is the mass rate of flow of a polymerthrough a specified capillary under controlled conditions of temperatureand pressure. It is typically measured according to ASTM 1238.

This invention provides a polymeric blend that is a marriage of apolyamide such as nylon 6 and an ionomer selected from a special familyof ionomers (denoted anhydride ionomers) to provide materials that arehighly suitable for polymeric backsheets for PV modules. In essence, thenew materials overcome some of the major deficiencies of both polyamidesand ionomers, while continuing to retain most of the desirableattributes. As indicated above, the ionomers used in this invention areselected from a family of ionomers containing dicarboxylic acidmoieties, or derivatives thereof. As used herein, the term “anhydrideionomer” is used to describe an ionomer that includes dicarboxylic acidmoieties, derivatives thereof such as anhydrides or other knowncarboxylic acid derivatives. The presence of dicarboxylic acid moietiesin the ionomers enhances the compatibility with polyamides, particularlyat higher levels, and provides blends with very good toughness, lowtemperature impact strength and resistance to hydrolytic delamination.Higher amounts of dicarboxylic acid moieties provide two unique featuresto blends of such ionomers and a polyamide, such as nylon 6. First, theanhydride ionomer is dispersed in the polyamide in extremely fineparticles and second, the particle size distribution is very narrow.

As indicated above, this invention provides a backsheet for a PV modulecomprising a thermoplastic composition comprising a polyamide and anionomeric composition comprising or consisting essentially of acopolymer of ethylene, an alpha,beta-unsaturated C₃-C₈ carboxylic acid,at least one comonomer that is an ethylenically unsaturated dicarboxylicacid or derivative thereof, and optionally at least one comonomerselected from alkyl acrylate and alkyl methacrylate.

Ionomeric resins (“ionomers”) are ionic copolymers of an olefin such asethylene (E) with a metal salt of an unsaturated carboxylic acid, suchas acrylic acid (AA), methacrylic acid (MAA), and/or other acids, andoptionally softening comonomers. At least one alkali metal, transitionmetal, or alkaline earth metal cation, such as lithium, sodium,potassium, magnesium, calcium, or zinc, or a combination of suchcations, is used to neutralize some portion of the acidic groups in thecopolymer resulting in a thermoplastic resin exhibiting enhancedproperties. For example, a copolymer of ethylene and acrylic acid canthen be at least partially neutralized to salts comprising one or morealkali metal, transition metal, or alkaline earth metal cations to forman ionomer. Copolymers can also be made from an olefin such as ethylene,an unsaturated carboxylic acid and other comonomers such as alkyl(meth)acrylates providing “softer” resins that can be neutralized toform softer ionomers.

The ionomers useful in this invention consist of a family of ionomerscontaining dicarboxylic acid moieties that can be derived fromethylenically unsaturated derivatives of dicarboxylic acid comonomers,such as maleic anhydride and ethyl hydrogen maleate, at least partiallyneutralized by one or more alkali metal, transition metal, or alkalineearth metal cations (denoted as anhydride ionomers). They are copolymersof ethylene, an α,β-unsaturated C₃-C₈ carboxylic acid and at least onecomonomer that is an ethylenically unsaturated dicarboxylic acid at anamount of from 0.5 weight % to 12 weight %, alternatively from 3 weight% to 12 weight %. Preferably, the dicarboxylic acid comonomer(s) arepresent in an amount from 4 weight % to 10 weight %. The unsaturateddicarboxylic acid comonomers or their derivatives can be selected from,for example, maleic anhydride (MAH), ethyl hydrogen maleate (also knownas maleic acid monoethylester—MAME), and itaconic acid (ITA). Morepreferably, a copolymer comprises from 4 to 8 weight % of maleic acidmonomethylester comonomer in an ethylene/methacrylic acid/maleic acidmonomethylester copolymer wherein from 20 to 70 percent of the totalacid groups in the copolymer are neutralized to provide carboxylatesalts containing alkali metal, transition metal, or alkaline earth metalcations.

Some non-neutralized ethylene acid copolymers comprising lower amountsof ethylenically unsaturated dicarboxylic acid comonomers are known (seeU.S. Pat. No. 5,902,869), as are their ionomeric derivatives (see U.S.Pat. No. 5,700,890).

As indicated above, comonomers such as alkyl (meth)acrylates can beincluded in the ethylene acid copolymer to form a copolymer that can beneutralized to provide carboxylate salts with alkali metal, alkalineearth metal or transition metal cations. Preferred are comonomersselected from alkyl acrylate and alkyl methacrylate wherein the alkylgroups have from 1 to 8 carbon atoms, and more preferred are comonomersselected from methyl acrylate, ethyl acrylate, iso-butyl acrylate (iBA),and n-butyl acrylate (nBA). The alkyl (meth)acrylates are optionallyincluded in amounts from 0 to 30 weight % alkyl (meth)acrylate such as0.1 to 30 weight % when present and preferably from 0.1 to 15 weight %of the copolymer.

Examples of copolymers useful in this invention include copolymers ofethylene, methacrylic acid and ethyl hydrogen maleate (E/MAA/MAME) andcopolymers of ethylene, acrylic acid and maleic anhydride (E/AA/MAH).

Neutralization of the ethylene acid copolymer can be effected by firstmaking the ethylene acid copolymer and treating the copolymer withinorganic base(s) with alkali metal, alkaline earth metal or transitionmetal cation(s). The copolymer can be from 10 to 99.5% neutralized withat least one metal ion selected from lithium, sodium, potassium,magnesium, calcium, barium, lead, tin, zinc, aluminum; or combinationsof such cations. Neutralization may be from 10 to 70%. Preferably thecopolymer has from 20%, alternatively from 35%, to 70% of the availablecarboxylic acid groups ionized by neutralization with at least one metalion selected from sodium, zinc, lithium, magnesium, and calcium; andmore preferably zinc or sodium. Notably the carboxylic acidfunctionalities present are at least partially neutralized tocarboxylate salts comprising zinc or sodium, preferably zinc. Ofparticular note is an anhydride ionomer comprising zinc as theneutralizing cation.

Mixed metal ionomers may provide a combination of better properties tothe blends with polyamides than ionomers comprising a single type ofcation. For example, a zinc/sodium mixed ion ionomer blended withpolyamide may provide lower water sorption, better scratch resistanceand better processing capability than those provided by a correspondingionomer containing only an alkali metal such as sodium. The zinc/sodiummixed ion ionomer may also provide higher hardness and higher mechanicalstrength than provided by a corresponding ionomer containing only zinc.Mixed ion ionomers are conveniently prepared by blending an ionomercomposition with a single cation, such as a zinc-containing ionomer,with an ionomer with a different cation, such as a sodium-containingionomer. Alternatively, mixed ion ionomers may be prepared byneutralizing an acid copolymer with different neutralizing agents,either sequentially or simultaneously.

Methods for preparing ionomers from copolymers are well known in theart.

Of note are blends of polyamides and anhydride ionomers furthercomprising conventional ionomers prepared from acid copolymers notcontaining a dicarboxylic acid or derivative. Accordingly, compositionsof this invention include blends of polyamide with component (2) furthercomprising in combination with the anhydride ionomer one or moreconventional ionomer comprising an E/X/Y copolymer where E is ethylene,X is a C₃ to C₈ α,β-ethylenically unsaturated monocarboxylic acid, and Yis a comonomer selected from alkyl acrylate and alkyl methacrylatewherein the alkyl groups have from 1 to 8 carbon atoms, wherein X ispresent in from 2 to 30 weight % of the E/X/Y copolymer, Y is presentfrom 0 to 40 weight % of the E/X/Y copolymer, wherein the carboxylicacid functionalities present are at least partially neutralized by oneor more alkali metal, transition metal, or alkaline earth metal cations.Preferred α,β-ethylenically unsaturated monocarboxylic acids includeacrylic acid and methacrylic acid. Non-limiting, illustrative examplesof conventional ionomers include E/15MAA/Na, E/19MAA/Na, E/15AA/Na,E/19AA/Na, E/15MAA/Mg, E/19MAA/Li, and E/15MAA/60Zn (wherein Erepresents ethylene, MAA represents methacrylic acid, AA representsacrylic acid, the numbers represents either the weight % of comonomer(s)present in the copolymer or the amount of neutralization of theavailable carboxylic acid groups, and the atomic symbol represents theneutralizing cation).

Depending on the need of a particular application, the amount of suchconventional ionomer or mixture of conventional ionomers in combinationwith the anhydride ionomer in component (2) can be manipulated toprovide an appropriate balance of toughness, low temperature impactstrength and resistance to hydrolytic delamination. For example, highlytoughened polyamide compositions can be achieved by using relativelylarger amounts of conventional ionomers with smaller amounts ofanhydride ionomers (for example, 30 weight % of conventional ionomer and6 weight % of anhydride ionomer). Toughened polyamide films can beprepared using relatively larger amounts of anhydride ionomers withsmaller amounts of conventional ionomers (for example, 30 weight % ofanhydride ionomer and 6 weight % of conventional ionomer). Of note aremodifier blends comprising equal amounts of anhydride ionomer andconventional ionomer (for example, 18 weight % of anhydride ionomer and18 weight % of conventional ionomer). When a conventional ionomer isblended with an anhydride ionomer, the blend desirably contains combinedamounts of each of the comonomers within the ranges described in theSummary of the Invention for the ionomeric copolymer.

Notably, when the polyamide is poly(caprolactam) (nylon-6), the ionomercomponent consists of an anhydride ionomer.

The polyamide-ionomer blend may comprise, consist essentially of consistof or be produced from, a polyamide in an amount from a lower limit of53, 58 or 60 weight % to an upper limit of 64 weight % and an anhydrideionomer in an amount from a lower limit of 36 or 40 weight % to an upperlimit of 42, or 47 weight %, all based on the weight of the combinationof polyamide and anhydride ionomer.

Polyamides (abbreviated herein as PA), also referred to as nylons, arecondensation products of one or more dicarboxylic acids and one or morediamines, and/or one or more aminocarboxylic acids such as11-aminododecanoic acid, and/or ring-opening polymerization products ofone or more cyclic lactams such as caprolactam and laurolactam.Polyamides may be fully aliphatic or semiaromatic.

Polyamides from single reactants such as lactams or amino acids,referred to as AB type polyamides are disclosed in Nylon Plastics(edited by Melvin L. Kohan, 1973, John Wiley and Sons, Inc.) and includenylon-6, nylon-11, nylon-12, or combinations of two or more thereof.Polyamides prepared from more than one lactam or amino acid includenylon-6,12.

Other well-known polyamides useful in the composition include thoseprepared from condensation of diamines and diacids, referred to as AABBtype polyamides (including nylon-66, nylon-610, nylon-612, nylon-1010,and nylon-1212), as well as from a combination of lactams, diamines anddiacids such as nylon-6/66, nylon-6/610, nylon-6/66/610, nylon-66/610,or combinations of two or more thereof.

Fully aliphatic polyamides used in the composition are formed fromaliphatic and alicyclic monomers such as diamines, dicarboxylic acids,lactams, aminocarboxylic acids, and their reactive equivalents. In thiscontext, the term “fully aliphatic polyamide” also refers to copolymersderived from two or more such monomers and blends of two or more fullyaliphatic polyamides. Linear, branched, and cyclic monomers may be used.

Carboxylic acid monomers comprised in the fully aliphatic polyamidesinclude, but are not limited to aliphatic dicarboxylic acids, such asfor example adipic acid (C6), pimelic acid (C7), suberic acid (C8),azelaic acid (C9), decanedioic acid (C10), dodecanedioic acid (C12),tridecanedioic acid (C13), tetradecanedioic acid (C14), andpentadecanedioic acid (C15). Diamines can be chosen among diamines withfour or more carbon atoms, including but not limited to tetramethylenediamine, hexamethylene diamine, octamethylene diamine, decamethylenediamine, dodecamethylene diamine, 2-methylpentamethylene diamine,2-ethyltetramethylene diamine, 2-methyloctamethylenediamine;trimethylhexamethylenediamine, meta-xylylene diamine, and/or mixturesthereof.

Semi-aromatic polyamides include a homopolymer, a copolymer, aterpolymer or more advanced polymers formed from monomers containingaromatic groups. One or more aromatic carboxylic acids may beterephthalic acid or a mixture of terephthalic acid with one or moreother carboxylic acids, such as isophthalic acid, phthalic acid,2-methyl terephthalic acid and naphthalic acid. In addition, the one ormore aromatic carboxylic acids may be mixed with one or more aliphaticdicarboxylic acids, as disclosed above. Alternatively, an aromaticdiamine such as meta-xylylene diamine (MXD) can be used to provide asemi-aromatic polyamide, an example of which is MXD6, a homopolymercomprising MXD and adipic acid.

Preferred polyamides disclosed herein are homopolymers or copolymerswherein the term copolymer refers to polyamides that have two or moreamide and/or diamide molecular repeat units. The homopolymers andcopolymers are identified by their respective repeat units. Forcopolymers disclosed herein, the repeat units are listed in decreasingorder of mole % repeat units present in the copolymer. The followinglist exemplifies the abbreviations used to identify monomers and repeatunits in the homopolymer and copolymer polyamides:

HMD hexamethylene diamine (or 6 when used in combination with a diacid)T Terephthalic acid

6-Caprolactam

AA Adipic acidDDA Decanedioic acidDDDA Dodecanedioic acidI Isophthalic acidMXD meta-xylylene diamineTMD 1,4-tetramethylene diamine6T polymer repeat unit formed from HMD and TMXD6 polymer repeat unit formed from MXD and AA66 polymer repeat unit formed from HMD and AA610 polymer repeat unit formed from HMD and DDA612 polymer repeat unit formed from HMD and DDDA11 polymer repeat unit formed from 11-aminoundecanoic acid12 polymer repeat unit formed from 12-aminododecanoic acid

In the art the term “6” when used alone designates a polymer repeat unitformed from ∈-caprolactam. Alternatively “6” when used in combinationwith a diacid such as T, for instance 6T, the “6” refers to HMD. Inrepeat units comprising a diamine and diacid, the diamine is designatedfirst. Furthermore, when “6” is used in combination with a diamine, forinstance 66, the first “6” refers to the diamine HMD, and the second “6”refers to adipic acid. Likewise, repeat units derived from other aminoacids or lactams are designated as single numbers designating the numberof carbon atoms.

In various embodiments the polyamide comprises one or more polyamidesselected from among the following groups (wherein PA is shorthand forpolyamide or “nylon”):

Group I polyamides have a melting point of less than 210° C., andcomprise an aliphatic or semiaromatic polyamide such aspoly(hexamethylene dodecanediamide/hexamethylene terephthalamide)(PA612/6T). See PCT Patent Application Publication WO2011/94542. Group Ipolyamides may have semiaromatic repeat units to the extent that themelting point is less than 210° C. and generally the semiaromaticpolyamides of the group have less than 40 mole percent of semiaromaticrepeat units. Semiaromatic repeat units are defined as those derivedfrom monomers selected from one or more of the group consisting ofaromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphaticdiamines having 4 to 20 carbon atoms. Other notable Group I polyamidesinclude PA6/66, PA6/610, PA6/66/610, PA6/6T, PA1010, PA11 and PA12.

Group II polyamides have a melting point of at least 210° C. andcomprise an aliphatic polyamide. Notable Group II polyamides includePA6, PA66, PA610 and PA612. The RV of PA6 is commonly measured accordingto ISO Test Method 307 using a solution of 1% of polymer in 96% sulfuricacid. The RV of PA66 is commonly measured according to ISO Test Method307 using a solution of 1% of polymer in 90% formic acid.

Group III polyamides have a melting point of at least 210° C. andcomprise

(aa) 20 to 35 mole percent semiaromatic repeat units derived from one ormore monomers selected from

(i) aromatic dicarboxylic acids having 8 to 20 carbon atoms andaliphatic diamines having 4 to 20 carbon atoms; and

(bb) 65 to 80 mole percent aliphatic repeat units derived from one ormore monomers selected from

(ii) an aliphatic dicarboxylic acid having 6 to 20 carbon atoms and analiphatic diamine having 4 to 20 carbon atoms; and

(iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms.

A preferred Group III polyamide is PA66/6T.

Group IV polyamides have a melting point of greater than 230° C. andcomprise

(cc) 50 to 95 mole percent semiaromatic repeat units derived from one ormore monomers selected from

(i) aromatic dicarboxylic acids having 8 to 20 carbon atoms andaliphatic diamines having 4 to 20 carbon atoms; and

(dd) 5 to 50 mole percent aliphatic repeat units derived from one ormore monomers selected from

(ii) an aliphatic dicarboxylic acid having 6 to 20 carbon atoms and saidaliphatic diamine having 4 to 20 carbon atoms; and

(iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms.

A preferred Group IV polyamide is PA6T/66.

Group V polyamides have a melting point of at least 260° C. and comprise

(ee) greater than 95 mole percent semiaromatic repeat units derived fromone or more monomers selected from

(i) aromatic dicarboxylic acids having 8 to 20 carbon atoms andaliphatic diamines having 4 to 20 carbon atoms; and

(ff) less than 5 mole percent aliphatic repeat units derived from one ormore monomers selected from

(ii) an aliphatic dicarboxylic acid having 6 to 20 carbon atoms and saidaliphatic diamine having 4 to 20 carbon atoms; and

(iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms.

A preferred Group V Polyamide is PA6T/DT.

Group VI polyamides have no melting point and include poly(hexamethyleneisophthalamide/hexamethylene terephthalamide) (PA6I/6T) andpoly(hexamethylene isophthalamide/hexamethyleneterephthalamide/hexamethylene hexanediamide) (PA6I/6T/66).

In various embodiments the polyamide is a Group I polyamide, Group IIpolyamide, Group III polyamide, Group IV polyamide, Group V polyamide orGroup VI polyamide, respectively.

Preferred polyamides include PA6, PA66, PA610, PA612, PA6/66, PA6/610,PA6/66/610, PA6/6T, PA610/6T, P612/6T, PA1010, PA11, PA12 andcombinations thereof. More preferred polyamides include PA6, PA66,PA610, PA612, PA610/6T, PA612/6T, PA1010, PA11, PA12 and combinationsthereof, including PA6, PA612, P612/6T or PA12, with PA6 most preferred.

The polyamide component may also be a blend of two or more polyamides.Preferred blends include those selected from the group consisting ofGroup I and Group II polyamides, Group I and Group III polyamides, GroupI and Group VI polyamides, Group II and Group III polyamides, Group IIand Group IV polyamides, Group II and Group V polyamides, Group II andGroup VI polyamides, Group III and Group VI polyamides, and Group IV andGroup V polyamides. A notable blend is a blend of PA612 and PA612/6T,especially in a blend ratio of 1:3 of PA612:PA612/6T. See U.S. PatentApplication Publication 2012/0196973.

Polyamides and processes for making them are well known to those skilledin the art, so the disclosure of which is omitted in the interest ofbrevity.

The polyamide may have a relative viscosity (RV) of 2.5 to 4.0,preferably from 2.6 to 3.5. Relative viscosity is related to meltviscosity. Varied methods may be used for measured RV values, and notall commercial polyamides list the RV values. RV is determined bycomparing the time required for a specific volume of polymer solution toflow through a capillary tube with the corresponding flow time of thesame volume of pure solvent. Different solvents may be used, dependingon the polyamide of interest. Common solvents include 96% sulfuric acidand 90% formic acid. For example, the RV of nylon-6 is measured using 1%in 96% sulfuric acid according to ISO Test Method 307. A similar methodfor determining RV is according to ASTM D789.

Grades of nylon-6 targeted for extrusion (such as Ultramid® B33 fromBASF) with RV of around 3.3 are suitable. Molding grades of nylon-6(such as Ultramid® B27 from BASF) with RV of around 2.7 are alsosuitable for this application.

The polyamide-ionomer blend further contains 0 to 20 weight % ofpigment; and 0 to 40 weight % of filler; such that the pigment and/orfiller comprises 8 to 50 weight % of the total composition.

As used herein pigments have refractive indices greater than 1.8,preferably greater than 2, and particle size less than 0.5 microns suchas 0.2 to 0.4 microns. The compositions may comprise inorganic pigmentssuch as oxide pigments, e.g., titanium dioxide, zinc oxide, and antimonyoxide. Other pigments include lithophone, chromomolybdic acid, sulfideselenium compound, ferrocyanide and carbon black pigments. Notably, thepigment comprises titanium dioxide, zinc oxide, or antimony oxide,preferably titanium dioxide. The compositions containing inorganicpigments maintain good flowability and color the molded article evenwhen used in a small amount.

As used herein fillers have refractive indices of 1.6 or less andparticle size of 0.8 micron or greater. Suitable fillers include mineralfillers such as inorganic oxides, carbonates, sulfates, silicas, alkaliand alkaline earth metal silicates, and barytes of a metal of Groups IA,HA, IIIA, IIB, VIB or VIII of the periodic table of the elements,including magnesium silicates such as talc (Mg₃Si₄O₁₀(OH)₂),wollastonite (CaSiO₃), phyllosilicates (mica) and calcium carbonate.Notably, the filler comprises an inorganic oxide, carbonate, sulfate,silica, alkali and alkaline earth metal silicate, or baryte of a metalof Groups IA, HA, IIIA, IIB, VIB or VIII of the periodic table of theelements, preferably wherein the filler comprises calcium carbonate,barium sulfate, wollastonite and talc, more preferably talc. Fillers mayoptionally be coated such as with silane treatments to improve wettingbetween the filler and the polymer matrix. The shape, size, and sizedistribution of the filler all impact its effectiveness as filler,though, at high levels, the particular characteristics of the fillerbecome less important. Preferably the filler particles have a ratio ofthe largest dimension to the smallest dimension greater than 5. Fillersalso include glass fibers. Desirably, fillers provide stiffening(improving Young's modulus ASTM D882) and reduce the coefficient oflinear thermal expansion (ASTM E831) for the composition whilemaintaining good elongation to break (ASTM D882). Large particles suchas those having a particle size in at least one dimension greater than200 microns such as mica or glass fibers provide good stiffening but canreduce elongation to break. Particles with at least one dimension lessthan 20 microns or less than 5 microns are preferred. Talc (plate likefillers) and Wollastonite (rod like fillers) provide for minimizingco-efficient of linear thermal expansion, maximizing stiffness, whilestill maintaining a reasonable amount of elongation to break. Preferablythe fillers are either transparent, such as glass fibers, or white toproduce whiter compositions. For example, talc commercially available asJetfine® 3CA is whiter than Jetfine® 3CC, which when incorporated intothe polymer matrix leads to a whiter composition. This is particularlydesirable when used in combination with a white pigment such as titaniumdioxide.

For example but not limitation, the composition may comprise 8 to 20weight % of pigment such as TiO₂ and 0 weight % filler, or thecomposition may comprise 8 to 40 weight % of filler such as talc and 0weight % of pigment, or the composition may comprise 10 to 40 weight %of filler such as talc and 8 to 15 weight % of pigment. Notablecompositions comprise or include 8 to 12 weight % of pigment and 12 to18 weight % of filler such as 10 weight % of pigment and 15 weight % offiller.

The polyamide-ionomer blend may further contain additional additivesthat provide weatherability, stability or improved processing. Thepolyamide-ionomer composition or blend can comprise 0.1 to 5 weight % ofoptional additives, based on the weight of the total composition. Suchadditives include stabilizers, antioxidants, ultraviolet ray absorbers,hydrolytic stabilizers, antistatic agents, fire-retardants, processingaids such as lubricants, antiblock agents, release agents, orcombinations of two or more thereof. Of particular note are oxidationinhibitors (antioxidants), UV stabilizers and hindered amine lightstabilizers. The relative percentages of these additives may be varieddepending upon the particular use of the object desired. The additivescan be added to the polymer blend in typical melt compounding equipment.

Suitable stabilizers include antioxidants, such as the Irganox® familyproduced by Ciba-Geigy (now a part of BASF), and UV stabilizers such asthose sold under the Tinuvin® tradename by Ciba-Geigy or Cyasorb® lightstabilizer and light absorber produced by Cytec. Preferred antioxidantsare based on hindered phenols, and preferred UV stabilizers are based onhindered amine light stabilizers (HALS) such as those sold under theChimassorb® tradename from BASF.

Lubricants of note include salts of fatty acids such as sodium stearateor zinc stearate, which may be added at 0.1 to 1 weight % of the totalcomposition.

The blend may also contain phosphorous salts such as a hypophosphitesalt. Suitable phosphorous salts for use in the blends are described ingreater detail in U.S. Pat. No. 6,399,684. The salts, including sodium,lithium, or potassium hypophosphite may be added to the blendcomposition in 0.1 to 3 weight % of the composition. Hypophosphite saltsmay provide improved morphological or physical properties to the blendsuch as increased Vicat temperature and/or improved tensile properties.Of note is a composition as described herein consisting essentially of(1) a polyamide as described above; (2) an ionomer as described above;and (3) hypophosphite salt.

The polymeric blend composition may be mixed with pigment, filler and/oradditional additives using well known melt mixing methods employingextruders or other suitable mixers such as Banbury or Farrel continuousmixers or roll mills.

Embodiments of the composition include:

The composition wherein the polyamide component comprises nylon 6, nylon12, nylon 610, nylon 612, nylon 610/6T, nylon 612/6T, or combinationsthereof.The composition wherein the polyamide component comprises nylon 6.The composition wherein the comonomer of (c) is a C₁-C₄ alkyl half esterof maleic acid.The composition wherein the carboxylic acid functionalities present areat least partially neutralized to carboxylate salts comprising zinc orsodium.The composition wherein the carboxylic acid functionalities present areat least partially neutralized to carboxylate salts comprising zinc.The composition wherein the anhydride ionomer component furthercomprises in combination with the anhydride ionomer one or more ionomercomprising an E/X/Y copolymer where E is ethylene, X is a C₃ to C₈α,β-ethylenically unsaturated monocarboxylic acid, and Y is a comonomerselected from alkyl acrylate and alkyl methacrylate wherein the alkylgroups have from 1 to 8 carbon atoms, wherein X is present in from 2 to30 weight % of the E/X/Y copolymer, Y is present from 0 to 40 weight %of the E/X/Y copolymer, wherein the carboxylic acid functionalitiespresent are at least partially neutralized to carboxylate saltscomprising one or more alkali metal, transition metal, or alkaline earthmetal cations.The composition 1 comprising 8 to 20 weight % of pigment and 0 weight %filler.The composition comprising 8 to 40 weight % of filler and 0 weight % ofpigment.The composition comprising 10 to 40 weight % of filler and 8 to 15weight % of pigment.The composition comprising 8 to 12 weight % of pigment and 12 to 18weight % of filler.The composition wherein the pigment comprises titanium dioxide.The composition wherein the filler comprises an inorganic oxide,carbonate, sulfate, silica, alkali and alkaline earth metal silicate, orbaryte of a metal of Groups IA, IIA, IIIA, IIB, VIB or VIII of theperiodic table of the elements.The composition wherein the filler comprises calcium carbonate, bariumsulfate, wollastonite or talc.The composition wherein the filler comprises talc.The composition comprising 10 to 40 weight % of talc and 8 to 15 weight% of titanium dioxide.The composition embodying any combination of the above embodiments.

Once the polyamide-ionomer blends are prepared as described above, theycan be further processed into monolayer or multilayer structures usefulas a backsheet for a photovoltaic module. Molten extruded thermoplasticcompositions can be converted into film or sheet using any techniquesknown to one skilled in the art. Suitable additional processes includewithout limitation blown film extrusion, cast film extrusion, cast sheetextrusion, lamination, coextrusion, extrusion coating, and the like. Anotable multilayer backsheet structure may comprise a layer comprising ablend of polyethylene and ionomer adjacent to the encapsulant layer ofthe photovoltaic module.

Embodiments of the backsheet comprise any of the compositions describedabove. Notable embodiments include:

The backsheet wherein the polyamide component comprises nylon 6.The backsheet wherein the pigment comprises titanium dioxide.The backsheet wherein the filler comprises calcium carbonate, bariumsulfate, wollastonite or talc.The backsheet wherein the filler comprises talc.The backsheet wherein the polyamide-ionomer blend composition comprises10 to 40 weight % of talc and 8 to 15 weight % of titanium dioxide.

A film or sheet can be further oriented beyond its immediate quenchingor casting. The process comprises the steps of (co)extruding a laminarflow of molten polymers, quenching the (co)extrudate and orienting thequenched (co)extrudate in at least one direction. The film may beuniaxially oriented, or it can be biaxially oriented by drawing in twomutually perpendicular directions in the plane of the film to achieve asatisfactory combination of mechanical and physical properties.Orientation and stretching are well known to one skilled in the art andthe description of which is omitted herein for the interest of brevity.

For multilayer structures, the layers may be coextruded or they may beformed independently and then adhesively attached to one another to formthe backsheet. A backsheet can be made by (co)extrusion optionallyfollowed by lamination onto one or more other layers. The backsheet maybe fabricated by extrusion coating or laminating some or all of thelayers onto a substrate. For example, a sheet or film of a core layermay be produced, to which skin layers and optional tie layers areadhered. Some backsheet structures contain “e-layers” or layers thathave a special affinity to adhere to the encapsulant. The e-layers canbe co-extruded, or laminated to the subject backsheet compositionthrough the use of a coextrudable adhesive. However, additional e-layersare not required to be coated or laminated onto the instant backsheetstructures. The polyamide-ionomer alloys that comprise the backsheethave strong adhesion to encapsulant layers, such as the standardcommercial EVA encapsulant materials, without additional e-layers.

A sheet could be further processed by thermoforming into a shapedarticle. In thermoforming, a flat sheet is heated above its softeningpoint and stretched to the desired shape. For example, a sheetcomprising the polyamide-anhydride ionomer composition could bethermoformed into a shape that conforms to the shape of the photovoltaicelements in the photovoltaic cell.

For use as a backsheet in a photovoltaic module, the thickness of thesheet is desirably 8 to 20 mils (200 to 500 microns).

A laminated solar cell module of the invention comprises or consistsessentially of a frontsheet providing a front support layer formed of alight transmitting material and having first and second surfaces; aplurality of interconnected solar cells having a first surface facingthe front support layer and a second surface facing away from the frontsupport layer; a transparent encapsulant surrounding and encapsulatingthe interconnected solar cells, the transparent encapsulant being bondedto the second surface of the front support layer; and a backsheet asdescribed above wherein one surface of the backsheet is bonded to thesecond surface of the transparent encapsulant.

The frontsheet or incident layer may be derived from any suitable sheetsor films. Suitable sheets may be glass or polymeric sheets, such asthose comprising a polymer selected from polycarbonates, acrylics,polyacrylates, cyclic polyolefins (e.g., ethylene norbornene polymers),polystyrenes (preferably metallocene-catalyzed polystyrenes),polyamides, polyesters, fluoropolymers, or combinations of two or morethereof.

The term “glass” includes not only window glass, plate glass, silicateglass, sheet glass, low iron glass, tempered glass, tempered CeO-freeglass, and float glass, but also colored glass, specialty glass (such asthose containing ingredients to control solar heating), coated glass(such as those sputtered with metals (e.g., silver or indium tin oxide)for solar control purposes), E-glass, Toroglass, Solex® glass (PPGIndustries, Pittsburgh, Pa.) and Starphire® glass (PPG Industries). Suchspecialty glasses are disclosed in, e.g., U.S. Pat. Nos. 4,615,989;5,173,212; 5,264,286; 6,150,028; 6,340,646; 6,461,736; and 6,468,934. Itis understood, however, that the type of glass to be selected for aparticular module depends on the intended use.

For example, fluoropolymer films, such as ethylene-tetrafluoroethylenecopolymer (ETFE) films, may be used as frontsheets in photovoltaicmodules instead of the more common glass layers. Another alternative isa film made from a perfluorinated copolymer resin such as atetrafluoroethylene-hexafluoropropylene copolymer (FEP).

The light-receiving side of the solar cell layer may sometimes bereferred to as a front side and in actual use conditions would generallyface a light source. The non-light-receiving side of the solar celllayer may sometimes be referred to as a lower or back side and in actualuse conditions would generally face away from a light source.

Monocrystalline silicon (c-Si), poly- or multi-crystalline silicon(poly-Si or mc-Si) and ribbon silicon are the materials used mostcommonly in forming the more traditional wafer-based solar cells.Photovoltaic modules derived from wafer-based solar cells often comprisea series of self-supporting wafers (or cells) that are solderedtogether. The wafers generally have a thickness of between 180 and 240μm.

The solar cell layer may be significantly thicker than the other layersand irregular in shape and/or thickness, including spaces between andaround the solar cells and other components of the solar cell layer. Inthis connection, it should be noted that the conductors thatinterconnect the solar cells commonly are arranged to form stress reliefloops to compensate for expansion and contraction caused by temperaturechanges. Those loops need to be encapsulated with the cells. However,when a polymeric backsheet is used, care must be taken to make certainthat the stress loops will not pierce the backsheet when the severallayers are compressed under heat to form the laminated module.Penetration of the backsheet by one or more stress loops will promoteearly failure of the module, e.g., by short-circuiting resulting fromingress of moisture at the point(s) of stress loop penetration thebacksheet.

Therefore, portions of the backsheet laminate will contact theencapsulant layer outside the perimeter of the solar cell layer and canbe adhered when heat is applied. As used herein, the perimeter of thesolar cell layer is the outline of the outer limits of the areaencompassed by the solar cell layer. In many cases, it is desirable thatthe encapsulant material flows into the spaces and closely encapsulatesthe solar cells and other components to physically consolidate thephotovoltaic module. Thus, it may be necessary to apply heat for aperiod of time sufficient to allow such flow, which may be longer thanthat needed for adhering thinner layers of a more regular shape. Forexample, heat may be applied in such a manner that the assembly ismaintained above the softening point of the encapsulant layer for 5 to30 minutes to effectively consolidate the photovoltaic module.

The encapsulant layers used in preparing photovoltaic modules describedherein may each comprise a polymeric material independently selectedfrom olefin unsaturated carboxylic acid copolymers, ionomers of olefinunsaturated carboxylic acid copolymers, ethylene vinyl acetatecopolymers, poly(vinyl acetals) (including acoustic grade poly(vinylacetals)), polyurethanes, polyvinylchlorides, polyethylenes (e.g.,linear low density polyethylenes), polyolefin block copolymerelastomers, copolymers of α-olefins and ethylenically unsaturatedcarboxylic acid esters (e.g., ethylene methyl acrylate copolymers andethylene butyl acrylate copolymers), silicone elastomers, epoxy resins,or combinations of two or more thereof.

The encapsulant layer may preferably comprise a thermoplastic polymerincluding ethylene vinyl acetate copolymers, olefin unsaturatedcarboxylic acid copolymers, ionomers of olefin unsaturated carboxylicacid copolymers, and combinations thereof (for example, a combination oftwo or more olefin unsaturated carboxylic acid copolymers, a combinationof two or more ionomers of olefin unsaturated carboxylic acidcopolymers, or a combination of at least one unsaturated carboxylic acidcopolymer with one or more ionomers of unsaturated carboxylic acidcopolymers).

The solar cell module and assembly to prepare it may optionally furthercomprise other functional film or sheet layers (e.g., dielectric layersor barrier layers) embedded within the module. Such functional layersmay be derived from any of the above mentioned polymeric films or thosethat are coated with additional functional coatings. For example,poly(ethylene terephthalate) films coated with a metal oxide coating,such as those disclosed in U.S. Pat. Nos. 6,521,825 and 6,818,819 andEuropean Patent EP1182710, may function as oxygen and moisture barrierlayers in the laminates.

If desired, a layer of nonwoven glass fiber (scrim) may also be includedbetween the solar cell layers and the encapsulants to facilitatedeaeration during the lamination process or to serve as reinforcementfor the encapsulants. The use of such scrim layers is disclosed in,e.g., U.S. Pat. Nos. 5,583,057; 6,075,202; 6,204,443; 6,320,115; and6,323,416 and European Patent EP0769818.

In addition, metal films, such as aluminum foil or metal sheets, such asaluminum, steel, galvanized steel, or ceramic plates may be utilized inaddition to the polymeric backsheet described herein as backing layersfor the photovoltaic module.

A special film or sheet may be included to serve both the function of anencapsulant layer and an outer layer. It is also conceivable that any ofthe film or sheet layers included in the module may be in the form of apre-formed single-layer or multilayer film or sheet.

If desired, one or both surfaces of the incident layer films and sheets,the backsheet films and sheets, the encapsulant layers and other layersincorporated within the solar cell module may be treated prior to thelamination process to enhance the adhesion to other laminate layers.This adhesion enhancing treatment may take any form known in the art andincludes those set forth in U.S. Patent Application Publication2010/0108126.

Manufacturing the solar cell module comprises providing a front supportlayer formed of a light transmitting material and having front and backsurfaces; placing a first transparent thermoplastic encapsulant layeradjacent to the back surface of the front support layer; positioning aplurality of interconnected solar cells having first and second surfacesso that the first surfaces thereof are adjacent to the first transparentencapsulant layer; placing a second transparent thermoplasticencapsulant layer adjacent to the second surfaces of the solar cells;placing a backsheet as described above adjacent to the secondtransparent thermoplastic encapsulant layer to thereby form an assembly;subjecting the assembly to heat and pressure so as to melt theencapsulant layers and cause the encapsulant to surround the solarcells, and cooling the assembly so as to cause the encapsulant tosolidify and bond to the front support layer, the solar cells and thebacksheet, thereby laminating the layers and the solar cells together toform an integrated solar cell module.

The photovoltaic module is prepared by providing an assembly forconversion under heat and pressure into a laminated solar cell module,the assembly comprising a front support layer formed of a lighttransmitting material and having front and back surfaces; a firsttransparent thermoplastic encapsulant layer adjacent to the back surfaceof the front support layer; a plurality of interconnected solar cellshaving first and second surfaces adjacent to the first transparentencapsulant layer; a second transparent thermoplastic encapsulant layerdisposed adjacent to the solar cells in parallel relation to the firsttransparent encapsulant layer; and a thermoplastic backsheet layer asdescribed above.

A vacuum laminator may be used to adhere the layers of the assemblytogether to provide the photovoltaic module. The laminator comprises aplaten base, on which the layers of the assembly are placed inoverlaying fashion for lamination. The laminator also comprises anenclosure that covers and completely surrounds the platen base. Theregion enclosed by the platen and enclosure may be evacuated. Thelaminator also comprises a flexible bladder within the enclosureattached to the top inner surface of the enclosure, which may beinflated to a pressure greater than the pressure in the evacuatedregion. For example, the pressure above the bladder may be atmosphericand the laminate may be held under vacuum beneath the bladder to removeair. When the bladder is inflated, the flexible surface of the bladderis pushed from the top of the enclosure toward the platen and applies asurface pressure to the multilayer assembly to ensure a good thermalcontact between the assembly and the platen. For lamination of themodule, the laminator is preheated to a temperature above the softeningtemperature of the encapsulant layer(s) and held at that temperaturethroughout the lamination process.

Heat-resistant sheets may be placed under the assembly to retard heatflow and allow deaeration and devolatilization of the sample. Releasesheets may be placed under the and/over the assembly to prevent thesample layers from adhering to parts of the laminator. The assembly isplaced on the platen and the enclosure of the laminator is lowered intoplace and sealed. Next, the region surrounding the assembly between theplaten and enclosure of the laminator is evacuated (e.g. to a pressureof 1 mbar) to help further with the prevention of voids, defects, andair pockets. Next, the rubber bladder is inflated (e.g. to a pressure of999 mbar) so that it presses against the assembly and ensures goodthermal contact with the platen. The pressure and heat are maintainedfor a sufficient period of time (for 1 to 10 minutes) to soften theencapsulant layers and adhere to solar cells and the adjoining layers.

When the heating step is complete, the bladder is depressurized to 0mbar so that it may be removed from contact with the multilayer filmlaminate, the enclosure is vented to atmospheric pressure and theenclosure is unsealed and opened. The multilayer film laminate isremoved from the platen and allowed to cool to room temperature.

The lamination methodology described here is by no means the onlypossible way to carry out such laminations. For example, more advancedlaminators have retractable pins that hold the multilayer laminatestructure above the heat source until the desired time to effect contactand heating. This would obviate the need for heat resistant layers inmost cases.

EXAMPLES Materials Used

AI-1: A copolymer of ethylene, 11 weight % of methacrylic acid and 6weight % of ethyl hydrogen maleate, neutralized with Zn cations to alevel of 50-60%, MI of 0.1 g/10 minAI-2: an anhydride ionomer terpolymer comprising ethylene, 13 weight %of acrylic acid and 4 weight % of ethyl hydrogen maleate neutralizedwith Zn cations to a level of 50%.ION-1: A copolymer of ethylene and 19 weight % of methacrylic acid,neutralized with Zn cations to a level of about 36%, MI of 1.3 g/10 minION-2: A copolymer of ethylene and 15 weight % of methacrylic acid,meutralized with Zn cations to a level of about 60%, MI of 0.7 g/10 minPA-6: nylon-6 homoploymer available commercially as Ultramid® B27E fromBASF.PA-12A: nylon-12 homopolymer available commercially as Rilsan® AMNO fromArkema.PA-12B: nylon-12 homopolymer available commercially as Rilsan® AESNOfrom Arkema.PA-612/6T: nylon-612/6T copolymer available from DuPont under thetradename Zytel®.Tie-1: a maleic anhydride modified linear low density polyethylene(LLDPE), with density of 0.91 g/cm³ and melt index of 1.7 g/10 min,commercially available from DuPont.Tie-2: a maleic anhydride modified linear low density polyethylene(LLDPE), with density of 0.91 g/cm³ and melt index of 2.7 g/10 min,commercially available from DuPont.Tie-3: a maleic anhydride modified linear low density polyethylene(LLDPE), with density of 0.91 g/cm³ and melt index of 3.1 g/10 min,commercially available from DuPont.TiO₂: titanium dioxide commercially available from DuPont as Ti-Pure®R105 or comparable material.TiO₂ Concentrate: 70 weight % titanium dioxide pre-dispersed in ethylenemethacrylate copolymer commercially available as 111676 White COP MBfrom Ampacet (660 White Plains Road, Tarrytown, N.Y. 10591).ZnO Concentrate: 45 weight % zinc oxide pre-dispersed in ethylenemethacrylic acid copolymer.Fillers used are summarized in the following table.

bulk true Particle Diameter Length density density Filler materialCommercial designation shape (μm) (μm) (kg/m³) (kg/m³) F1 wollastoniteNyglos ® 8 rod 12 156 480 2900 F2 coated wollastonite Nyglos ® 8 10012rod 12 156 480 2900 F3 wollastonite Nyglos ®G rod 55 825 720 2900 F4mica Suzorite ® 60S platy 150-500 176-291 2700 F5 glass fibersChopvantage ® HP3660 fiber 10 3000-4000 2460 F6 talc Jetfine ® 3CA White1 platy F7 talc Jetfine ® 3CC Tan 1 platy F8 talc Luzenac ® HAR-T84platy 2Additives used are summarized in the following table.

Commercial Additive function material designation Add1 lubricant zincstearate Commercial grade Add2 UV absorber oxanilide Tinuvin ® 312 Add3UV light HALS Tinuvin ® 770 stabilizer Add4 UV light HALS Chimassorb ®440 stabilizer Add5 antioxidant phenolic antioxidant Irganox ® B1171 andphosphite Add6 antioxidant phenolic antioxidant Irganox ® 1010 Add7antioxidant phenolic antioxidant Irganox ® B215 and phosphite Add8processing trisarylphosphite Irgafos ® 168 stabilizer Add9 antioxidantphenolic antioxidant Irganox ® 1098 Add10 UV light HALS Chimassorb ® 944stabilizer Add11 UV absorber Oxanilide Tinuvin ® 234 Add12 processingSodium hypophosphite Commercial grade stabilizer Add13 lubricant Zincstearate Commercial grade

Several commercial backsheet structures were evaluated as standards:

HRPET: Hydrolysis resistant PET, 12 mil thickness, commerciallyavailable as PYE3000 from Coveme SPA, Bologna, Italy.TPT: Tedlar®/PET/Tedlar®, 12 mil thickness, commercially available asIcosolar® 2442 from Isovoltaic AG, Leibring, Austria or 1200 Dun-solarTPT backsheet, commercially available from DUNMORE Corporation, 145Wharton Rd., Bristol, Pa. 19007.APA: A three-layer sheet comprising a core layer comprising polyesterand two skin layers comprising modified polyamide, commerciallyavailable as Icosolar® APA 4004 from Isovoltaic AG, Liebring, Austria.AAA: A three-layer sheet comprising a core layer comprising modifiedpolyamide and two skin layers comprising modified polyamide,commercially available as Icosolar® AAA 3554 from Isovoltaic AG,Liebring, Austria.

Blends of materials listed above were prepared by melt blendingfollowing the procedure described or similar processes. Compounding wasdone using a 25 mm 38/1 L/D ZSK-25 World Lab twin-screw extrudercomprised of nine 100 mm long barrels manufactured by Krupp Werner &Pfleiderer (Coperion) or similar processes. The polymers werepre-blended and then fed to the throat of the extruder (barrel 1) usinga K-tron® loss-in-weight feeder. The fillers were fed using a secondK-tron® feeder to the extruder using a side feeder at Barrel 4. Therewas a vacuum pulled on the melt before and after addition of the filler(at barrel 4 and barrel 8). The melt blend exiting the extruder die face(after barrel 9) was die face-cut using a Gala cutter.

Operating conditions for Comparative Example C4 in Table 2 are shown inTable 1. Other examples were prepared similarly.

TABLE 1 Set Point (° C.) Actual (° C.) Temperature Control Zone 1uncontrolled (Barrel 1 feed) Temperature Control Zone 1 260 260 (BarrelZones 2 and 3) Temperature Control Zone 2 260 260 (Barrel Zones 4 and 5)Temperature Control Zone 3 260 260 (Barrel Zones 6 and 7) TemperatureControl Zone 4 260 257 (Barrel Zones 8 and 9) Temperature Control Zone 5260 257 (Die) Screw RPM 300 Torque % 53% Die pressure (Mpa)     5.3 (770psig) Melt Temperature ° C. 297 Feed rate polymer 95 gpm Feed ratefiller 40 gpm Vacuum (mm Hg) Zone 4 and 8 51 KPa (15 in Hg)

The compositions of the melt blends are shown in Table 2.

TABLE 2 Filler Example Loading PA6 ION-2 AI-1 F1 F2 F3 F4 C1  0% 60% 40%C2  0% 60% 40% C3 15% 51% 34% 15% 1 15% 51% 34% 15% C4 30% 42% 28% 30% 230% 42% 28% 30% 3 40% 36% 24% 40% 4 30% 42% 28% 30% 5 40% 36% 24% 40% C515% 51% 34% 15% 6 15% 51% 34% 15% C6 30% 42% 28% 30% 7 30% 42% 28% 30%

The collected pellets were dried overnight at 70 to 85° C. in anair-circulating Blue M tray dryer oven that was fitted with a nitrogenpurge. Each of the dried polymer samples were used to cast 8-inch (228mm) wide, nominally 0.33 to 0.35 mm thick sheets. Sheets were cast usinga 31.75-mm diameter 30/1 L/D single screw extruder, built by WayneMachine (Totowa, N.J.), fitted with a 3/1 compression ratio,single-flight screw with 5 L/D of a melt mixing section. The extruderdie was a 203-mm wide coat hanger type flat film die with a 0.35 mm diegap. The molten polymer film exiting from the die was cast onto a 203-mmwide by 203-mm diameter double shell spiral baffle casting roll fittedwith controlled temperature cooling water. The casting roll and die werebuilt by Killion Extruders (Davis Standard, Cedar Grove, N.J.). Extruderconditions typical for the compositions are provided in Table 3.

TABLE 3 Extruder Conditions Set Point (° C.) Actual (° C.) Barrel Zone 1240 240 Barrel Zone 2 240 240 Barrel Zone 3 240 240 Barrel Zone 4 240240 Filter Flange 240 240 Adapter 240 240 Die End 245 245 Flat Die 240240 Melt Temp (before filter) 237 Melt Temp (after filter) 240 MeltPress (MPa) before filter 4.6 (670 psig)

The 0.35-mm thick polymer sheets were used to test properties relevantto PV backsheets.

Test Methods

Ash: Samples were weighed into a crucible and heated for 15 minutes inan 800° C. muffle furnace. The reported number represents the % ofsample remaining in the crucible. This test was used to verify that theproper loading of filler was achieved.

Tensile Properties (ASTM D882-12) were measured on 25 mm by 150 mmcoupons die cut from the sheet. Five coupons were oriented so that thelong direction was in the machine direction (MD) and five coupons wereoriented so that the long direction was in the transverse direction(TD). Coupons were conditioned at 50% RH and 23° C. for at least sevendays prior to testing at 50% RH and 23° C. The gage length was 25 mm andthe cross-head speed was 508 mm/min. The reported results are theaverage of five coupons. A combination high Young's Modulus (measure ofstiffness) and at least 100% elongation (higher elongation suggestsbetter toughness) to break is preferred.

Coefficient of Linear Thermal Expansion (ASTM E813-13) was measured on4.9 by 65 mm coupons die cut from the sheet. Three coupons were orientedso that the long direction was in the MD and three coupons were orientedso that the long direction was in the TD. Coupons were conditioned at50% RH and 23° C. for at least seven days prior to testing. The thermalmechanical analyzer was set up with the film fiber probe and a 0.1 Npreload force was applied. Specimens were cooled to −60° C. prior to thestart of the run and the heated a rate of 5° C./min to 90° C. The slopeof the best fit linear line between −60° C. and 90° C. was taken as CLTE(μm/m/° C.). Two test results in each orientation are reported. A lowercoefficient of linear thermal expansion is preferred so that thethermoplastic backsheet expands and contacts the encapsulant layer.

Moisture Vapor Transmission Rate (MVTR) at 38° C. and 100% RH wasmeasured on coupons cut from sheet according to ASTM F1249.

Moisture Vapor Transmission Rate (MVTR) at 85° C. and 100% RH wasmeasured on a Permatran 3/33 model using a Yamato DKN402 oven. ASTMF1249-06, was followed except the temperature was 85° C.

Moisture Uptake at 50% RH and 23° C. or water immersion at 85° C. Thistest measured the amount of water absorbed into a sheet sample(typically 25 mm wide by 150 mm long) die cut from the sheet after theindicated exposure condition. Moisture absorbed was determined by KarlFischer titration as per ASTM D6869-03 (150° C. oven temperature).

Shrinkage after heat treating for 30 minutes in air-circulating oven at150° C. Rectangles were scissor cut from the sheet. Samples were allowedto condition at 50% RH and 23° C. for at least seven days prior tomeasuring sheet dimension in MD and TD. Samples were then suspended by ahook in a pre-heated air circulating oven at 150° C. for 30 minutesafter which the sheet samples were removed from the oven allowed tocondition for at least 48 hours at 50% RH and 23° C. before the MD andTD lengths were measured again. Changes in dimension are reported as thepercent reduction in the dimension as a result of conditioning at 150°C.

Color Measurement (ASTM E1347-06) Color of samples was measured using aHunter Lab Colorquest XE Colorimeter (L*, a*, b*). L* is a measure ofwhiteness; whiter materials have higher L* values.

Summaries of the test results are given in Tables 4 and 5.

TABLE 4 Tensile properties CLTE (ASTM D882-12) (μm/m/° C.) Young'sStrain at MD TD Modulus (ksi) break (%) Sample Sample Sample Sample MDTD MD TD 1 2 1 2 C1 82.8 83.6 507 451 248 232 232 225 C2 100 79 484 451C3 154 102 458 428 152 144 224 244 1 118 101 431 298 C4 249 108 162 19 2181 125 12.6 16.2 3 194 138 3.8 5.4 4 261 114 64 20.8 5 171 161 3.8 4.8C5 117.9 114 73.7 36 142 126 136 152 6 114.9 107.8 91 50 C6 178.8 177 96.6 7 163 141 9 8.2

The test results in Table 4 show that adding fillers increased stiffnessas measured by a higher Young's modulus and reduced toughness asmeasured by elongation or strain at break. Fillers also reduced theCoefficient of Linear Thermal Expansion and on a weight basis, biggerrodlike or platelike fillers reduce CLTE more. Comparative Example C1contained no filler and had CLTE greater than 200 μm/m/° C. ComparativeExample C3 containing 15 weight % of wollastonite had an MD CLTE of lessthan 155 μm/m/° C. and Comparative Example C5 containing 15 weight %mica had an MD CLTE of less than 142 μm/m/° C.

TABLE 5 Water Uptake at 23° C. shrinkage MVTR at 38° C. at in at 150° C.g-mm/m²/day g-mm/m²/day 50% RH water MD TD Sample 1 Sample 2 % % % % C195 99 2.5 7.3 0 0.3 C2 64 62 2.4 6.4 0.5 0.6 C3 72 70 5.6 0.2 1 1 62 615.3 0.5 0.7 C4 48 40 1.6 5.3 0.1 0.7 2 67 69 4.7 0.2 0.3 3 4.8 0.1 0.7 443 41 1.7 4.9 0 0.3 5 330 366 1.4 4.7 0 0 C5 54 51 2 5.4 0.5 0.3 6 63 632.1 5.6 0.2 0.3 C6 32 32 1.6 4.7 0.4 0 7 65 67 1.6 4.7 0 0

As shown in Table 5, the addition of fillers tended to reduce themoisture vapor transmission rate, with some exceptions. Example 5contained 40 weight % of mica and had a very high MVTR (higher than thesample that contained no filler). With small rod-shaped fillers, thepolyamide-anhydride ionomer examples had lower MVTR than comparablepolyamide-conventional ionomer compositions. With mica filler, theopposite was observed. The addition of filler can result in a reductionof the moisture uptake. In terms of shrinkage of the sheet after 30minutes at 150° C., all of the samples had very low shrinkage (with orwithout filler). These shrinkage numbers are very close to the error inthe measuring device.

The results in Tables 4 and 5 suggested bigger filler types (likefiberglass or mica) were better at reducing sheet CLTE and increasingsheet stiffness but resulted in very low elongation to break and hadnegative effect on moisture transmission.

Additional blends were prepared with additives as shown in Table 6.

TABLE 6 Blend A B C* D* E F* G H I J Material Weight % Blend A 83.9 73.9Blend C 90 85 PA-6 60 0 60 60 39.23 PA-12A 0 22 0 PA-12B 0 33 0 AI-1 4045 0 40 ION-1 40 31.36 ION-2 35.7 HDPE 53.54 ZnO 1.7 Conc. TiO₂ 15 15 1010 15 Talc 10 15 F6 10 Add1 0.7 Add2 0.2 Add3 0.15 0.6 Add5 0.2 0.3 0.28Add6 0.1 0.15 0.15 Add7 0.15 Add8 0.1 Add10 0.31 0.7 Add11 0.35 Add120.13 Add18 1.1 *Commercially available from LTL Color Compounders, Inc.20 Progress Drive, Morrisville, PA 19067. Additional UV stabilizer andantioxidant additives may also be present (not included in the weight%).

The blends in Table 6 were combined and melt blended with additionalmaterials to provide polyamide-ionomer compositions summarized in Table7 useful for PV backsheets. Other fillers were included such as talc.Example 10 has no filler but has 21.5 weight % of TiO₂ Concentrate as apigment.

TABLE 7 Filler Blend TiO₂ Loading A C G Concentrate F6 F7 Add2 Add3 Add5L* a* b* C7 0 100 C8 30 70 30  8 30 70 30 C9 15 85 15  9 15 85 15 1077.7 21.5 0.2 0.6 0.3 89.3 −0.2 3.3 11 15 84.2 15 0.2 0.6 0.3 47.5 1.13.1 12 25 74.3 25 0.2 0.6 0.3 58.6 −1.3 3.9 13 15 70.1 14.2 15 0.2 0.60.3 84.6 −0.9 3.3

The color of pellets of Compositions 10-13 was measured and the valuesindicated in Table 7. Compositions using talc filler F6 were whiter thanwith talc filler F7 as indicated by L*.

Tables 8 and 9 list the property tests on the sheet samples.

TABLE 8 Tensile properties (ASTM D882-12) CLTE (μm/m/° C.) Young'sModulus (MPa) Strain at break (%) MD TD MD TD MD TD Sample 1 Sample 2Sample 1 Sample 2 C7 548 566 560 533 212 202 194 205 C8 1426 1197 200186 80 77 96 97 8 1257 1248 326 297 C9 963 856 377 395 126 112 151 138 9944 783 453 440 HRPET 2141 2158 135 114 588.1 584.5 205 224.8 TPT 31233241 101 81 33.08 33.96 25.15 25.8

The test results in Table 8 show that smaller platelike fillers liketalc can be added to the polyamide-ionomer blend at loadings as high as30 weight % to reduce the CLTE and still maintain at least 100%elongation to break. Polyamide-anhydride ionomer compositions hadroughly comparable stiffness and better strain at break than comparablepolyamide-conventional ionomer compositions. The compositions had lowerYoung's modulus and higher strain at break than commercial backsheetmaterials.

TABLE 9 MVTR at 38° C. Water uptake at 23° C. shrinkage at 150° C. AshTest (g-mm/[m²-day]) at 50% RH in water MD TD Sample 1 Sample 2 Sample 1Sample 2 % % % % C7 2 2 9.24 9.62 2.2 6.3 0.7 0.7 C8 31 31 1.88 1.88 1.44.2 0.2 0.5 8 30 30 1.75 1.75 1.5 4.4 0.1 0.5 C9 16 16 3.88 4.11 1.8 5.00.2 0.3 9 16 16 3.15 3.20 1.8 4.6 0.6 0.5 HRPET 0.786 0.2 1.4 1.0 0.3TPT 0.786 0.3 0.5 0.2 0.0

In Table 9, significant reductions in MVTR and moisture absorption wereseen when fillers were added to the polyamide-ionomer blends. Example 8and Comparative Example C8 contained 30 weight % talc and had MVTR of 75or less and moisture absorption of less than 4.5 weight % at 85° C.compared to the non-filled blend (C7) that had an MVTR of over 300g-mil/m²/day and moisture absorption at 85° C. of 6.3%.Polyamide-anhydride ionomer compositions had roughly comparable wateruptake and lower MVTR than comparable polyamide-conventional ionomercompositions.

The next comparison illustrates that under equivalent compoundingconditions, better mechanical and thermal properties were obtained whenthe mineral filler was added to a nylon-6 polyamide-anhydride ionomeralloy compared to adding the mineral filler to a nylon-6polyamide-standard ionomer alloy.

TABLE 10 Weight % Thickness of sheet PA-6 ION-2 AI-1 Add8 Add9 F7 (mm)C10 44.80 30 0.10 0.1 25 0.35 10 44.80 30 0.10 0.1 25 0.34

The tensile properties were measured on film samples conditioned for oneweek at 23° C. and 50% RH and summarized in Table 11. Moisturepermeation, uptake and damp heat aging are also summarized in Table 11.

TABLE 11 C10 10 MD TD MD TD Tensile properties Young's Modulus 1113 9381150 896 (ASTM D882-12) (MPa) Strain at break (%) 136 42 319 280 CLTE(μm/m/° C.) 83.5 129 72.5 102 MVTR at 38° C. Transmittance 6.05 5.84(g/[m²-day]) Permeation 2.13 1.97 (g-mm/[m²-day]) Water uptake At 50% RH(%) 1.4 1.3 at 23° C. 1 week in water (%) 4.6 4.5 Strain Strain Young'sat Young's at Modulus break Modulus break Damp heat aging After 929 186853 319 at 85° C. and 72 hours 100% RH After 1001 51 1020 258 1000 hoursAfter 1028 50 1252 178 2000 hrs

As shown in Table 11, Young's Modulus was comparable for bothcompositions but the strain at break was significantly higher for thepolyamide-anhydride ionomer composition. The coefficient of linearthermal expansion was lower in both MD and TD for thepolyamide-anhydride ionomer composition. The permeation rate was lowerwith the polyamide-anhydride ionomer composition. The moisture pick-upafter 1 week at 50% RH or 1 week immersed in water was slightly lowerwith the polyamide-anhydride ionomer composition.

Table 11 also records the stiffness (Young's modulus) and elongation(strain at break) for the MD-oriented coupons after 72, 1000 and 2000hours of damp heat conditioning. The mineral-filled alloy based on thepolyamide-anhydride ionomer composition produced better hydrolysisresistance to damp heat aging than the one prepared with a conventionalionomer. The polyamide portion of the polyamide-ionomer alloy waspresumably undergoing further crystallization under the 85° C. and 100%RH conditioning so the observed stiffness (Young's Modulus) increasedwith time. Because hydrolysis and/or thermal degradation were alsooccurring there was a reduction in the amount of elongation in thecoupon before it broke. The coupons from the anhydride ionomer-polyamidecomposition exhibited much better retention of elongation to break overthis 2000-hour conditioning period.

Three-layer coextruded backsheet structures were prepared with thestructures summarized in Table 12. The term “outer skin” refers to thelayer of the backsheet structure that would face outward in thephotovoltaic module, the term “core” refers to a layer inside thebacksheet structure, and the term “inner skin” refers to the layer ofthe backsheet that would face the encapsulant layer of the photovoltaicmodule. The three-layer sheets were prepared from 15 weight %TiO₂-filled and 10 weight % talc-filled polyamide-ionomer compositions.The sheets were cast on a three layer coextrusion sheet line withnominally 0.002-inch (0.05 mm) thick skin layers and 0.010-inch (0.25mm) thick core layers. The sheet structures are given in Table 12.

TABLE 12 Outer skin layer Core layer Inner skin layer C11 Blend F BlendC Blend F C12 Blend F Blend D Blend F 11 Blend F Blend A Blend F C13Blend C Blend D Blend C 12 Blend C Blend A Blend C 13 Blend E Blend BBlend E

Tables 13 and 14 report the test results on the three-layer sheets.

TABLE 13 Tensile properties (ASTM D882-12) Young's Strain CLTE Modulus(MPa) at break (%) (μm/m/° C.) MD TD MD TD MD TD C11 717 703 495 505144.6 153.6 C12 800 727 446 459 114.1 138.3 11 624 591 414 470 186.9210.6 C13 816 770 462 444 48.8 125.5 12 619 639 502 472 13 627 577 395503 175.5 199.2 HRPET 2141 2158 135 114 586.3 227.9 TPT 3123 3241 101 8133.5 25.5

TABLE 14 Water uptake at 23° C. shrinkage at 150° C. Thickness MVTR at85° C. At 50% RH At 100% RH MD TD (mil) (mm) g/[m²-day]) (g-mm/[m²-day])% % % % C11 14.5 0.368 250.93 92.33 1.7 5.6 0.5 0.9 C12 13.9 0.353213.68 75.43 1.6 4.8 0.1 0.5 11 1.8 5.8 0.0 0.7 C13 1.6 4.8 0.2 0.3 121.9 6.1 0.0 0.7 13 15.6 0.396 85.84 33.99 0.9 2.1 0.1 0.7 HRPET 12 0.3050.2 1.4 1.0 0.3 TPT 13 0.330 36.5 12.04 0.3 0.5 0.2 0.0

Example 13 showed very good (low) water vapor transmission and uptakecompared to Comparative Examples C11 and C12.

The following General Procedure was used to laminate backsheet materialsto glass and encapsulant sheets to test the properties of a photovoltaicmodule. For these tests no photovoltaic layer was included, butlaminations with photovoltaic layers could be performed similarly.

Glass: 4-mm thick annealed glass from Kingston Plate and Glass(Kingston, Ontario Canada)

Encapsulant sheet: 0.015 inch thick EVA (ethylene vinyl acetatecopolymer encapsulant sheet (Photocap® 15420 or 15295 sold by STRCorporation, 18 Craftsman Road, East Windsor, Conn. 06088 USA)

General Procedure for Fabricating Glass/Encapsulant/Backsheet Laminates

Rectangles of Glass/Encapsulant/Backsheet [2.5 inch by 5 inch (62 by 125mm) or 5 inch by 5 inch (125 by 125 mm)] were laminated. The backsheetsamples were dried overnight under vacuum at 30° C. prior to laminating.The glass was washed with soapy water and the layers assembled asfollows: glass/encapsulant/backsheet/10 mil thick fluoropolymer coatedcloth/0.25-inch silicone rubber. If the backsheet contained an innerskin layer, that layer was in contact with encapsulant. One-inch (25 mm)wide tabs of fluoropolymer-coated release sheet were placed between theglass and the encapsulant and the encapsulant and the backsheet. Theinclusion of fluoropolymer release sheets provided a tab between glassand encapsulant or backsheet and encapsulant to initiate subsequent peeltesting on laminated glass. The assembly was placed in a 12 inch by 9inch (300 mm by 225 mm) vacuum bag (Tyvek® barrier bag Part numberSI-BA-7033, supplied by Smith Induspac Ltd 140 Iber Road, Stittsville,Ontario, Canada K2S 1E9). The assembly was vacuum sealed in the bagusing a Promarks TC-420LC vacuum sealer (Promarks, Inc., 1915 E. AcaciaStreet, Ontario, Calif. 9176, USA) with 60 seconds of vacuum prior toheat seal, seal time 2 seconds, cooling time 2.1 seconds. The layerswere thermally bonded together by placing the vacuum-bagged assembly ina preheated air-circulating oven set at 150° C. for 30 minutes. A 2.6 kgaluminum block was placed on top of the vacuum bag to improve theconsistency of the glass laminate. The glass side of the laminate wasdown during the thermal bonding. After 30 minutes in the oven, thevacuum bag assembly was removed and allowed to cool 10 minutes beforecutting open the bag and removing the laminate.

Adhesion: Peel tests were performed using 4 inch/minute (100 mm/mincrosshead speed after conditioning at 23° C., 50% RH. The glass is heldin place by the stationary jaw on the test machine. A tab from thebacksheet is gripped in the moving jaw. Test results are reported as theaverage of four peels for each material. Table 15 reports the averagepeel strength between the weakest interface (backsheet to encapsulant)or (encapsulant to glass).

TABLE 15 Adhesion to Encapsulant lb-f/in N/cm Location of peel C11 32 56Backsheet to encapsulant C12 40 70 Combination of backsheet toencapsulant and glass to encapsulant 11 40.5 71 Backsheet to encapsulantC13 13 23 Backsheet to encapsulant HRPET 10 18 Backsheet to encapsulantTPT 21 37 Glass-encapsulant

These peel strength numbers demonstrate a strong bond between backsheetand encapsulant which confirms the polyamide/ionomer alloy sheet doesnot require any special surface treatment to achieve a strong bond tothe EVA based encapsulant.

Test sheets were also fabricated into small photovoltaic modules havinga 2×2 array of solar cells. The components are listed in Table 16. Thematerials were laid up in the proper positions to prepare a functionalphotovoltaic module and laminated using a Meier vacuum laminator withlamination conditions of 145° C., for fifteen minutes, evacuation 3minutes and press for 11 minutes.

TABLE 16 Material Brand Code EVA Revax R767-0.45 mm thickness Solar cellJA Mono-125SOR22B 17.6-17.8% Solder Ribbon Sveck Sn62 Pb36 Ag2 Glass AGCJapan Solar grade --temper glass--low-Iron A1 Frame Haida 304 × 284 × 25mm Junction Box Renhe PV-RH06-60 Seal silicon Tonsan PV1527 Flux AsahiANX-3133Testing after Sheets were Used to Fabricate Mini Solar Modules

Damp heat: Two modules of each state were exposed to 85° C./85% RH forafter 0, 1000 and/or 2000 hours of damp heat exposure. Changes in coloron the front side (color through the glass) and back side of module weremeasured as described above.

UV testing: Using the IEC 61215 UV preconditioning standard (3% UVB),one module was exposed from the front and one from the back. Tests wereconducted after 0, 1, 2, 3, 4 and 5 times the IEC standard duration.

Thermal cycling (TC): Two modules of each state were exposed to cyclesof −40° C. to 85° C. per the IEC 61215 standard. Standard properties(see below) were measured after 0, 200, 400 and 600 cycles.

Thermal cycling-humidity freeze (TC-HF): Two modules of each state wereexposed to the IEC 61215 protocol of 50 cycles thermal cycling (−40° C.to 85° C.) followed by 10 cycles of humidity freeze (−40° C. to 85° C.at 85% RH). Standard properties after 0, 1, 2 and 3 intervals of 50thermal and 10 humidity freeze cycles were measured. Testing was doneafter the humidity freeze portion of the cycling. In the Tables below,the number of each type of cycle is indicated.

Table 17 reports testing on mini modules that were fabricated using thebacksheets in Table 12.

TABLE 17 Crack behavior Change in module color after 1000 hours dampheat treatment after after after ΔL* front ΔL* back Δb* front Δb* back150TC/20HF TC400 TC150/HF30 C11 3.6 0.6 −18.0 −3.6 Yes No Yes C12 4.00.3 −20.1 −3.0 No No No 11 2.1 0.4 −10.1 −2.7 Yes Yes Yes C13 4.0 0.4−18.6 −3.5 No No No 12 13 1.8 0.2 −2.5 −3.3 Yes Yes Yes HRPET 0.1 0.3−1.8 −0.4 No No No TPT 0.8 0.0 −1.3 −0.4 No No No

After 1000 hours of damp heat conditioning at 85° C. and 85% RH, it wasfound that looking through the front glass, certain modules hadyellowed. It was found the yellowness was due to yellowing of theencapsulant and not the backsheet. As shown in Table 17, small changesin the b color value were noted on the back side (−3 b shift) but largechanges in the b value were noted for the front side on certain modules.It was also found that cracks were appearing on selected backsheets inthe modules treated with periods of thermal cycling and freezing afterhigh humidity exposure.

Comparing the available MVTR data in Table 14, there is a correlationbetween the observed yellowing of the encapsulant and the MVTR. LowerMVTR corresponds to less yellowing. Cracking was not observed for minimodules fabricated from sheets with polyamide-ionomer formulations thatcontained talc.

Additional backsheets were prepared according to Table 18. Blend K inTable 18 is a mixture of 85 weight % of a 65:35 blend of high densitypolyethylene and ION-1 and 15 weight % of TiO₂ and UV stabilizersavailable from Mosaic Color and Additives, 110 Sulphur Springs Road,Greenville, S.C. under the commercial designation M002132WTPEP. Thesheets were tested for MVTR at 85° C. and 100% relative humidity asdescribed in the following procedure. MVTR was estimated by measuringthe weight loss of water filled, flanged aluminum cups lidded with thebacksheet in an 85° C. air circulating oven. To minimize bulging of thebacksheet from the water vapor pressure at 85° C., an 80 mesh stainlesssteel screen supported the backsheet on the non-water side of the cup.Backsheet and mesh screen were fixed in place by a retaining ring thatbolted to the flange of the aluminum cup. The weight loss (water loss)from the cup was measured each day over the course of seven days.Typically after 24 hours of conditioning at 85° C., the daily mass losswas consistent. The average daily mass loss was then corrected for thesurface area of the lidding backsheet to estimate the transmission rate.Each backsheet was tested in duplicate and the average of two measuresreported. The nominal dimensions of the inside of the flanged aluminumcups, was diameter 76 mm and the depth 50 mm. The cups were typicallyhalf filled with water (150 ml of water added to the cup).

TABLE 18 MVTR Outer skin layer Tie layer Core layer Tie layer Inner skinlayer (g/[m²-day]) 14 50 μm Blend E — 250 μm Blend 10 30 μm Tie-2 50 μmBlend K 56 15 50 μm Blend E — 250 μm Blend 12 30 μm Tie-2 50 μm Blend K46 16 300 μm Blend 13 — — 30 μm Tie-2 50 μm Blend K 44 C14 300 μm BlendJ — — 30 μm Tie-2 50 μm Blend K 49 17 300 μm Blend 13 — — 30 μm Tie-1 50μm Blend K 57 C15 300 μm Blend J — — 30 μm Tie-1 50 μm Blend K 66 18200-250 μm Blend I — — 25-50 μm Tie-2 50-75 μm Blend H 56 19 50-55 μmBlend I 40-50 μm Tie-3 150-200 μm Blend I 40-50 μm Tie-3 50-55 μm BlendI

1. A polyamide-ionomer blend composition comprising (i) A polymercomponent comprising 1) 53 to 64 weight %, based on the combination of(1) and (2), of a polyamide component; 2) 36 to 47 weight %, based onthe combination of (1) and (2), of an anhydride ionomer componentcomprising a copolymer of (a) ethylene; (b) from 5 weight % to 15 weight% of an alpha, beta-unsaturated C3-C₈ carboxylic acid; (c) from 0.5weight % to 12 weight % of at least one comonomer that is anethylenically unsaturated dicarboxylic acid or derivative thereofselected from maleic acid, fumaric acid, itaconic acid, maleicanhydride, or a C₁-C₄ alkyl half ester of maleic acid; and (d) from 0weight % to 30 weight % of monomers selected from alkyl acrylate oralkyl methacrylate, wherein the alkyl groups have from one to twelvecarbon atoms; wherein the carboxylic acid functionalities present are atleast partially neutralized to carboxylate salts comprising one or morealkali metal, transition metal, or alkaline earth metal cations; (ii) 0to 20 weight % of pigment; and (iii) 0 to 40 weight % of filler; and(iv) 0 to 5 weight % of weathering additives selected from oxidationinhibitors, UV stabilizers and hindered amine light stabilizers.
 2. Thecomposition of claim 1 wherein the combination of (ii) and (iii)comprises 8 to 50 weight % of the combination of (i), (ii), (iii) and(iv).
 3. The composition of claim 1 wherein the polyamide componentcomprises nylon 6, nylon 12, nylon 610, nylon 612, nylon 610/6T, nylon612/6T, or combinations thereof.
 4. The composition of claim 1 whereinthe polyamide component comprises nylon
 6. 5. The composition of claim 1wherein the comonomer of (c) is a C₁-C₄ alkyl half ester of maleic acid.6. The composition of claim 1 wherein the carboxylic acidfunctionalities present are at least partially neutralized tocarboxylate salts comprising zinc or sodium.
 7. The composition of claim5 wherein the carboxylic acid functionalities present are at leastpartially neutralized to carboxylate salts comprising zinc.
 8. Thecomposition of claim 1 comprising 8 to 20 weight % of pigment and 0weight % filler.
 9. The composition claim 1 comprising 8 to 40 weight %of filler and 0 weight % of pigment.
 10. The composition of claim 1comprising 10 to 40 weight % of filler and 8 to 15 weight % of pigment.11. The composition of claim 1 comprising 8 to 12 weight % of pigmentand 12 to 18 weight % of filler.
 12. The composition of claim 1 whereinthe pigment comprises titanium dioxide, zinc oxide, or antimony oxide.13. The composition of claim 1 wherein the filler comprises an inorganicoxide, carbonate, sulfate, silica, alkali and alkaline earth metalsilicate, or baryte of a metal of Groups IA, IIA, IIIA, IIB, VIB or VIIIof the periodic table of the elements.
 14. The composition of claim 13wherein the filler comprises calcium carbonate, barium sulfate,wollastonite or talc.
 15. The composition of claim 14 wherein the fillercomprises talc.
 16. The composition of claim 1 comprising 10 to 40weight % of talc and 8 to 15 weight % of titanium dioxide.
 17. Abacksheet for a photovoltaic module comprising the composition ofclaim
 1. 18. The backsheet of claim 17 wherein the polyamide componentcomprises nylon
 6. 19. The backsheet of claim 17 wherein the pigmentcomprises titanium dioxide, zinc oxide, or antimony oxide.
 20. Thebacksheet of claim 17 wherein the filler comprises calcium carbonate,barium sulfate, wollastonite or talc.
 21. The backsheet of claim 20wherein the filler comprises talc.
 22. The backsheet of claim 17 whereinthe polyamide-ionomer blend composition comprises 10 to 40 weight % oftalc and 8 to 15 weight % of titanium dioxide.
 23. A laminated solarcell module comprising a front support layer formed of a lighttransmitting material and having first and second surfaces; a pluralityof interconnected solar cells having a first surface facing the frontsupport layer and a second surface facing away from the front supportlayer; a transparent encapsulant surrounding and encapsulating theinterconnected solar cells, the transparent encapsulant being bonded tothe second surface of the front support layer; and a backsheet of claim17 wherein one surface of the backsheet is bonded to the second surfaceof the transparent encapsulant.
 24. An assembly for conversion underheat and pressure into a laminated solar cell module, the assemblycomprising a front support layer formed of a light transmitting materialand having front and back surfaces; a first transparent thermoplasticencapsulant layer adjacent to the back surface of the front supportlayer; a plurality of interconnected solar cells having first and secondsurfaces adjacent to the first transparent encapsulant layer; a secondtransparent thermoplastic encapsulant layer disposed adjacent to thesolar cells in parallel relation to the first transparent encapsulantlayer; and a thermoplastic backsheet of claim
 17. 25. A method ofmanufacturing a solar cell module comprising providing a front supportlayer formed of a light transmitting material and having front and backsurfaces; placing a first transparent thermoplastic encapsulant layeradjacent to the back surface of the front support layer; positioning aplurality of interconnected solar cells having first and second surfacesso that the first surfaces thereof are adjacent to the first transparentencapsulant layer; placing a second transparent thermoplasticencapsulant layer adjacent to the second surfaces of the solar cells;placing a backsheet of claim 17 adjacent to the second transparentthermoplastic encapsulant layer to thereby form an assembly; subjectingthe assembly to heat and pressure so as to melt the encapsulant layersand cause the encapsulant to surround the solar cells, and cooling theassembly so as to cause the encapsulant to solidify and bond to thefront support layer, the solar cells and the backsheet, therebylaminating the layers and the solar cells together to form an integratedsolar cell module.